Divinylsilane-terminated aromatic ether-aromatic ketone-containing compounds

ABSTRACT

A compound having the formula: 
     
       
         
         
             
             
         
       
     
     Each Ar is an aromatic group. Each R is an alkyl group. The value n is a positive integer. The values of w, x, y, and z are 0 or 1. If y is 0 than x and z are 0 and w is 1, and if y is 1 than x and z have different values and w equals z. A thermoset made by crosslinking a silane-containing compound with the above compound. A method of making the above compound when y is 1 by: reacting 4,4′-difluorobenzophenone with an aromatic diol to form an oligomer; and reacting the oligomer with a vinyl dialkylsilane. A method of making the below compound by: reacting 4,4′-difluorobenzophenone with a vinyl dialkylsilane. Each R is an independently selected alkyl group.

FIELD OF THE INVENTION

The invention is generally related to aromatic oligomers and productsmade therefrom.

DESCRIPTION OF RELATED ART

The rapid advancement of modern technology in recent years hasincreasingly demanded new high performance materials for use in a widevariety of engineering applications and under unusual serviceconditions. High temperature elastomers that have thermal,thermo-oxidative and hydrolytic stability above 300° C. (572° F.) andalso maintain flexibility to well below ambient temperature may besuitable for numerous marine and aerospace applications. Hightemperature, tough elastomers may be suitable for high voltageelectrical cables for advanced ships. Such elastomers may be suitablefor components in high flying airplanes and space vehicles, whichexperience extreme variations of temperatures from as low as −50° C. toas high as 300-350° C. Such crosslinked elastomers or networked systemsmay also be suitable for high temperature integral fuel tank sealants,which require long lasting elastomers (up to 10,000 hours) for use from−60° C. to 400° C. without swelling on contact with jet fuels but withexcellent adhesion and inertness toward metallic substrates.

SUMMARY OF THE INVENTION

The invention comprises a compound having the formula:

Each Ar is an independently selected aromatic group. Each R is anindependently selected alkyl group. The value n is a positive integer.The values of w, x, y, and z are 0 or 1. If y is 0 than x and z are 0and w is 1, and if y is 1 than x and z have different values and wequals z. The invention also comprises a thermoset made by crosslinkinga silane-containing compound with the above compound.

The invention also comprises a method comprising: reacting4,4′-difluorobenzophenone with an aromatic diol to form an oligomer; andreacting the oligomer with a vinyl dialkylsilane to form the abovecompound.

The invention also comprises a method comprising: reacting4,4′-difluorobenzophenone with a vinyl dialkylsilane to form a compoundhaving the below formula. Each R is an independently selected alkylgroup.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention will be readily obtainedby reference to the following Description of the Example Embodiments andthe accompanying drawings.

FIG. 1 shows TGA thermograms of a bisphenol A/benzophenone vinyl silanecured with CL-4 and postcured to 300° C. for 1 h. The resulting polymerswere heated under (A) nitrogen (top) and (B) air (bottom).

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

In the following description, for purposes of explanation and notlimitation, specific details are set forth in order to provide athorough understanding of the present invention. However, it will beapparent to one skilled in the art that the present invention may bepracticed in other embodiments that depart from these specific details.In other instances, detailed descriptions of well-known methods anddevices are omitted so as to not obscure the description of the presentinvention with unnecessary detail.

Efforts have been targeted towards developing high temperatureelastomers and flame resistant composites and addressing compositeprocessability issues based on cost effective manufacturing techniquessuch as resin transfer molding (RTM), resin infusion molding, andfilament winding. The work has been concerned with the incorporation ofunits within the backbone to enhance the flammability resistance andthermo-oxidative properties while retaining low temperatureprocessability. The liquid, low viscosity resin disclosed herein mayenable the deposition of a coating onto a substrate by typical coatingprocedures and composite processing by RTM and resin infusion methods.Furthermore, a low melt viscosity and a larger processing window may beuseful for fabrication of thick composite sections where the melt has toimpregnate thick fiber preforms. Most other high temperature resins arenot amenable to processing by cost effective methods such as RTM, resininfusion molding, and oven cure due to high initial viscosities, theevolution of volatiles during the cure, and or solvent-related problems.

The materials disclosed herein are related to the synthesis andpolymerization of oligomeric divinyl-terminated aromatic ether-aromaticketone-containing compounds, and their use as precursors to hightemperature elastomers/coatings, plastics, and ceramics. Hightemperature, tough, and clear elastomers that can be processed underambient conditions and that contain oligomeric aromatic ether-aromaticketone units between the polymerization centers are not known topreviously exist. These vinyl terminated units are interconnected byaromatic ether-aromatic ketone moieties with varying lengths to affectthe physical properties. Since the divinyl terminated oligomers may beviscous liquids and may be soluble in most organic solvents, they can befabricated into shaped elastomeric and plastic components or can bedeposited onto fibrous materials as coatings in the presence of a curingadditive. Polymerization can be achieved under ambient conditionreaction of the ketone unit with the curing additive containingmultiple—SiH units and by hydrosilation reactions involving the vinylterminated units. The incorporation of the aromatic units within thebackbone may enhance the stiffness, mechanical, thermal, and oxidativeproperties of the networked polymers fabricated from the materials.

The oligomeric aromatic ether-aromatic ketone-containing divinylterminated monomers may be polymerized stepwise through the ketone unitsand through the terminated vinyl groups to afford high temperature,flame resistant thermosets. Depending on the amount of curing additive,elastomers or plastics may be obtained from the novel oligomers.Reaction of both reactive sites (vinyl and ketone units) may afford ahighly crosslinked system. Polymeric coatings and composites formulatedfrom the oligomeric aromatic ether-aromatic ketone-containing divinylterminated monomers may have outstanding thermo-oxidative andflammability properties for military (ship, submarine, aerospace) anddomestic applications and can withstand continuous high temperatures(300-375° C.) in oxidative environments such as air for extendedperiods. The use of low molecular weight precursor resins to obtainthermosetting polymeric materials with high thermo-oxidative propertiesmay be advantageous from a processing standpoint. The precursor resinsmay be useful in composite fabrication by a variety of methods such asinfusion, resin transfer molding and prepreg consolidation. With the newoligomeric monomers of the present invention, processability to clearcoatings and shaped composite components can be achieved innon-autoclave conditions by cost effective methods.

One method for making the disclosed compounds is to react a4,4′-difluorobenzophenone with an aromatic diol to form an oligomer. Theoligomer may have any length and the reaction product will generallyhave more than one compound formed during the synthesis with the averagemolecular weight dependent on the ratios of reactants used. The mixturemay also include a compound containing single repeat unit of onereactant and none of the other. The reaction may be a nucleophilicreaction in the presence of K₂CO₃, N,N-dimethylformamide (DMF), andtoluene. This mixed solvent system allows the azeotropic distillation ofthe water formed as a by-product in the reaction at temperatures between135 and 145° C. Either the aromatic diol or the4,4′-difluorobenzophenone may be present in stoichiometric excess sothat the oligomer is terminated by the excess reactant. Reaction withexcess diol is shown in Eq. (3) and excess benzophenone is shown in Eq.(4). Suitable diols include, but are not limited to4,4′-dihydroxy-2,2-diphenylpropane (bisphenol A);1,1,1,3,3,3-hexafluoro-4,4′-dihydroxy-2,2-diphenylpropane (bisphenolA6F); biphenol, and resorcinol.

The oligomer may then be reacted with a vinyl dialkylsilane to addterminal vinyl silyl groups to the oligomer. When terminal diol is used,a chlorovinylsilane is used as in Eq. (5), and the reaction may beperformed in the presence of triethylamine and THF. When terminalbenzophenone is used, a vinylsilylphenol is used as in Eq. (6), and thereaction may be performed in situ with Eq. (4). Any unreactedbenzophenone may also be vinylsilyl terminated as shown in Eq. (7). Thepossible combinations for the values of w, x, y, and z are (0, 1, 1, 0),(1, 0, 0, 0), and (1, 0, 1, 1).

The reaction yields may be 91-95%. The vinyl-terminated oligomers of Eq.(1) may be readily soluble in common organic solvents such as toluene,DMF, acetone, methylene chloride, ether, and chloroform. The structuremay be confirmed by IR and ¹H-NMR spectroscopy. The length of the spacerbetween the terminal divinyl groups can be varied by changing the ratiobetween the diol and the benzophenone. The oligomeric divinyl resins maybe clear liquids, which may enhance their importance for coatingapplications.

The reaction of the vinyl-terminated oligomers with any compound (curingadditive) containing multiple SiH units may lead to a clearthermosetting polymer (elastomers and plastics). Thus, it is possible totailor the cured polymer according to specific needs. Suitable curingadditives include, but are not limited to,tetrakis(dimethylsiloxy)silane (CL-4); methyl tris(dimethylsiloxy)silane(CL-3 Me); phenyl tris(dimethylsiloxy)silane (CL-3 Ph);bis[(p-dimethylsilyl)phenyl]ether; diphenylsilane;1,1,3,3-tetramethyldisiloxane (CL-2);1,1,3,3,5,5,7,7-octamethyltetrasiloxane; and hydride-terminatedpolydimethylsiloxane. The thermoset may be made from more than oneoligomer, including oligomers differing in the value of 11. Thecrosslinked polymer may exhibit outstanding thermal and oxidativeproperties. FIG. 1 shows the thermograms of bisphenol A/benzophenonedivinyl silane cured with CL-4 up to 100° C. and postcured to 300° C.for 1 h. The polymer was stable to temperatures in excess of 300° C.When heated to 1000° C. under a flow of nitrogen and air, the polymershowed weight retention of 74% and 40%, respectively (FIG. 1). Thepolymer displayed a weight retention in air that was superior to otherhighly aromatic systems.

Upon addition of the curing additive at room temperature, the ketone andvinyl groups may commence to react as shown in Eq. (8). The ketone groupmay be more reactive. A thermoset formed from reaction of both theketone and the vinyl units with the silane groups would be highlycrosslinked. Thus depending on the curing conditions and thermalparameters, high temperature thermosetting soft-to-hardrubber-to-plastic-to-carbon/ceramic composition may be obtained.Regardless of the curing conditions, the liquid oligomericdivinyl-terminated aromatic ether-aromatic ketone-containing compoundsmay be converted to a thermoset or can be injected into afiber-reinforced perform for the fabrication of complex shaped compositecomponents. The thermosets (elastomers and plastics) or cured polymersmay show outstanding and superior thermo-oxidative properties. Theoverall physical properties may be tailored by varying the diol orbisphenol reactant. Regardless of whether the cured polymer is anelastomer or a plastic, clear shaped films or solids are formed, whichmay be useful for electronic, electrical, and structural applications.By using a less reactive catalyst in the cure reaction, the viscosity ofthe polymerization system may be easily controlled for extended periodsyielding a processing window, which may be advantageous for thefabrication of complex composite components and device coatings. Due tothe thermal and oxidative stability of thermoset or network polymerscured to temperatures in excess of 350° C., the materials have potentialfor a variety of applications including the fabrication of advancedcomposite components (ship, aerospace, and marine) by conventionalprepreg consolidation, RTM, injection molding, and filament winding andas a coating for electronic devices and for electrical insulator forhigh voltage cables. Due to the high char yield, the vinyl-basedpolymers of this invention may exhibit improvements in specific physicalproperties when used at high temperatures or in a fire environment. Thethermoset may also be formulated with a material such as, but notlimited to, carbon nanotubes, a clay, carbon nanofibers, a metal oxide,or microballoons. Microballoons are micron sized hollow glass beads.

The flexible aromatic ether units may maintain processability (liquid)in the oligomeric divinyl-terminated aromatic ether-aromaticketone-containing compounds and also contribute to high temperaturestability of polymers due to their own inherent thermal stability. Bycontrolling the ratio of reactants, different percentages of vinyl andaromatic ether-aromatic ketone units can be obtained in the resultingoligomeric compound. An ideal combination of reactants can be found toproduce a polymer tailored for a particular application.

Having described the invention, the following examples are given toillustrate specific applications of the invention. These specificexamples are not intended to limit the scope of the invention describedin this application.

Example 1

General synthesis method—The following method of making a 2:1 bisphenolA/benzophenone based hydroxyl terminated aromatic ether oligomer maygenerally be used for all the hydroxyl terminated aromatic etheroligomer syntheses by using appropriate diols and changing the reactantratio. More details may be found in Keller et al., U.S. Pat. No.7,087,707 (all referenced publications and patent documents areincorporated herein by reference). To a 250 mL three neck flask fittedwith a thermometer, Dean-Stark trap with condenser, and nitrogen inletis added bisphenol A (20.0 g, 87.6 mmol), 4,4′-difluorobenzophenone(9.56 g, 43.8 mmol), powdered K₂CO₃ (24.2 g, 175 mmol) andN,N-dimethylformamide (100 mL). After filling the Dean-Stark trap withtoluene and adding 5 mL to the reaction flask, the mixture is heated toreflux at 145° C. The water formed in the reaction is removed byazeotropic distillation. The mixture is refluxed for 9-12 hr until nomore water is observed being collected in the Dean-Stark trap. Theremaining toluene is then removed by distillation and the reactionmixture cooled to ambient temperature. The reaction mixture is pouredinto 300 mL of a 10% NaOH solution. The aqueous solution is extractedwith ether (2×100 mL) to remove impurities and the water layer madeacidic by the addition of 100 mL of 2 M HCl solution. The resultingmixture is extracted again with ether (2×100 mL) and the ether layerscombined. Carbon black (2 g) is added and the ether filtered through ashort plug of silica gel to remove any insoluble components. The solventis removed and the oil vacuum dried to yield the analytically pure 2:1hydroxy terminated oligomer as a yellow crystalline solid.

Example 2

Synthesis of 2:1 oligomeric vinyl silane terminated resin based onbisphenol-A and 4,4′-difluorobenzophenone—To a 100 mL three-necked flaskfitted with a thermometer, a Dean-Stark trap with condenser, and anitrogen inlet w ere added the 2:1 bisphenol A/benzophenone basedhydroxyl terminated aromatic ether oligomer (10.0 g, 15.7 mmol),triethylamine (4.72 ml, 33.9 mmol) and anhydrous tetrahydrofuran (100mL). The reaction mixture was cooled by means of an ice bath andvinyl(dimethylchloro)silane (4.68 ml, 33.1 mmol) was added dropwise. Theresulting mixture was stirred for 1 h. The mixture was poured into waterand extracted with diethyl ether. The solvent was removed in vacuo andthe resulting oil dissolved in 1:1 methylene chloride:hexane andfiltered through a silica plug. The solvent was removed in vacuo and theclear oil vacuum dried to yield the 2:1 oligomeric vinyl silaneterminated resin (11.5 g, 91%). IR [cm⁻¹]: δ 3052 (C═CH), 2967 (CH₃),1654 (C═O), 1593 (C═C), 1500 (aromatic), 1242 (C—O), 1171 (C—O), 834(aromatic).

Example 3

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy) silane (2:1 ratio, slow cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.36g) of Example 2 and tetrakis(dimethylsiloxy)silane (0.07 mL) wasdissolved in 1 mL of dry toluene. With stirring, a slow cure catalyst (7μL of 2-2.5% platinum-cyclovinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (5 min). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 4

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A and 4,4′-difluorobenzophenone andbis[(p-dimethylsilyl)phenyl]ether (2.5:1 ratio, slow cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.35g) of Example 2 and bis[(p-dimethylsilyl)phenyl]ether (0.05 g) wasdissolved in 1 mL of dry toluene. With stirring, a slow cure catalyst (7μL of 2-2.5% platinum-cyclovinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (15 min). The sample was postcured above 1000° C. to completely Cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 5

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A and 4,4′-difluorobenzophenone anddiphenylsilane (1:1 ratio, rapid cure)—A mixture formulated from the 2:1oligomeric vinyl silane terminated resin (0.50 g) of Example 2 anddiphenylsilane (0.11 g) was dissolved in 1 mL of dry toluene. Withstirring, a rapid cure catalyst (10 μL of 2-2.5%platinum-vinylmethylsiloxane complex in xylene solution) was added. Themixture was transferred to a silicone mold and was allowed to gel atroom temperature (5 min). The sample was post cured above 100° C. tocompletely cure (le resin. The result was a transparent elastomericsample which had good thermal and oxidative stability and retained >40%weight after heating under air to 1000° C.

Example 6

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A and 4,4′-difluorobenzophenone and1,1,3,3,5,5,7,7-octamethyltetrasiloxane (1:1 ratio, rapid cure)—Amixture formulated from the 2:1 oligomeric vinyl silane terminated resin(0.40 g) of Example 2 and 1,1,3,3,5,5,7,7-octamethyltetrasiloxane (0.14g) was dissolved in 1 mL of dry toluene. With stirring, a rapid curecatalyst (20 μL of 2-2.5% platinum-vinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (5 min). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 7

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy) silane (2.5:1 ratio, slow cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.38g) of Example 2 and tetrakis(dimethylsiloxy) silane (0.055 mL) wasdissolved in 1 mL of dry toluene. With stirring, a slow cure catalyst(10 IL of 2-2.5% platinum-cyclovinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (15 min). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 8

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy) silane (2.5:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.38g) of Example 2 and tetrakis(dimethylsiloxy) silane (0.055 mL) wasdissolved in 1 mL of dry toluene. With stirring, a rapid cure catalyst(10 μL of 2-2.5% platinum-vinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (10 seconds). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 9

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A and 4,4′-difluorobenzophenone and1,1,3,3-tetramethyldisiloxane (2.5:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.81g) of Example 2 and 1,1,3,3-tetramethyldisiloxane (0.17 mL) wasdissolved in 1 mL of dry toluene. With stirring, a rapid cure catalyst(25 μL of 2-2.5% platinum-vinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (1 mill). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 10

Synthesis of 2:1 oligomeric vinyl silane terminated resin based onbisphenol-A6F and 4,4′-difluorobenzophenone—To a 100 mL three-neckedflask fitted with a thermometer, a Dean-Stark trap with condenser, and anitrogen inlet were added the 2:1 bisphenol A6F/benzophenone basedhydroxyl terminated aromatic ether oligomer (10.0 g, 11.8 mmol),triethylamine (3.52 mil, 25.2 mmol) and anhydrous tetrahydrofuran (100mL). The reaction mixture was cooled by means of an ice bath andvinyl(dimethylchloro)silane (3.50 ml, 24.7 mmol) added dropwise. Theresulting mixture was stirred for 1 h. The mixture was poured into waterand extracted with diethyl ether. The solvent was removed in vacuo andthe resulting oil dissolved in 1:1 methylene chloride:hexane andfiltered through a silica plug. The solvent was removed in vacuo and theclear oil vacuum dried to yield the 2:1 oligomeric vinyl silaneterminated resin (11.0 g, 92%). IR [cm⁻¹]: δ 3051 (C═CH), 2968 (CH₃),1654 (C═O), 1590 (C═C) 1501 (aromatic), 1242 (C—O), 1171 (C—O), 833(aromatic).

Example 11

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A6F and 4,4′-difluorobenzophenoneand tetrakis(dimethylsiloxy)silane (3:1 ratio, rapid cure)—A mixtureFormulated from the 2:1 oligomeric vinyl silane terminated resin (0.33g) of Example 10 and tetrakis(dimethylsiloxy)silane (0.04 mL) wasdissolved in 1 mL of dry toluene. With stirring, a rapid cure catalyst(8 μL of 2-2.5% platinum-vinylmethylsiloxane complex in xylene solution)was added. The mixture was transferred to a silicone mold and wasallowed to gel at room temperature (10 seconds). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 12

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A6F and 4,4′-difluorobenzophenoneand phenyl tris(dimethylsiloxy)silane (1:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.21g) of Example 10 and phenyl tris(dimethylsiloxy)silane (0.09 mL) wasdissolved in 1 mL of dry toluene. With stirring, a rapid cure catalyst(20 μL of 2-2.5% platinum-vinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (10 seconds). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 13

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A6F and 4,4′-difluorobenzophenoneand methyl tris(dimethylsiloxy)silane (2:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.30g) of Example 10 and methyl tris(dimethylsiloxy)silane (0.037 mL) wasdissolved in 1 mL of dry toluene. With stirring, a rapid cure catalyst(10 μL of 2-2.5% platinum-vinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (5 seconds). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 14

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on bisphenol-A6F and 4,4′-difluorobenzophenoneand hydride terminated polydimethylsiloxane (1:2 ratio, rapid cure)—Amixture formulated from the 2:1 oligomeric vinyl silane terminated resin(0.14 g) of Example 10 and hydride terminated polydimethylsiloxane(MW˜450 g/mol) (0.16 g) was dissolved in 1 mL of dry toluene. Withstirring, a rapid cure catalyst (15 μL of a 2-2.5%platinum-vinyl-methylsiloxane complex in xylene solution) was added. Themixture was transferred to a silicone mold and was allowed to gel atroom temperature (1 minute). The sample was post cured above 100° C. tocompletely cure the resin. The result was a transparent elastomericsample which had good thermal and oxidative stability and retained >40%weight after heating under air to 1000° C. and a glass transitiontemperature below 0° C.

Example 15

Synthesis of 2:1 oligomeric vinyl silane terminated resin based onresorcinol and 4,4′-difluorobenzophenone—To a 100 mL three-necked flaskfitted with a thermometer, a Dean-Stark trap with condenser, and anitrogen inlet were added the 2:1 resorcinol/benzophenone based hydroxylterminated aromatic ether oligomer (10.0 g, 25.1 mmol), triethylamine(7.52 ml, 54.0 mmol) and anhydrous tetrahydrofuran (200 mL). Thereaction mixture was cooled by means of an ice bath andvinyl(dimethylchloro)silane (7.46 ml, 52.7 mmol) added dropwise. Theresulting mixture was stirred for 1 h. The mixture was poured into waterand extracted with diethyl ether. The solvent was removed in vacuo andthe resulting oil dissolved in 1:1 methylene chloride:hexane andfiltered through a silica plug. The solvent was removed in vacuo and theclear oil vacuum dried to yield the 2:1 oligomeric vinyl silaneterminated resin (13.4 g, 94%). IR [cm⁻¹]: δ 3052 (C═CH), 2970 (CH₃),1655 (C═O), 1593 (C═C), 1503 (aromatic), 1241 (C—O), 1170 (C—O), 834(aromatic).

Example 16

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on resorcinol and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy)silane (2.5:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.40g) of Example 15 and tetrakis(dimethylsiloxy)silane (0.13 mL) wasdissolved in 2 mL of dry toluene. With stirring, a rapid cure catalyst(25 μL of a 2-2.5% platinum-vinylmethylsiloxane complex in xylenesolution) was added. The mixture was transferred to a silicone mold andwas allowed to gel at room temperature (10 seconds). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Example 17

Formulation of carbon nanotube compositions from a catalytichydrosilylation reaction of 2:1 oligomeric vinyl silane terminated resinbased on bisphenol-A and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy)silane (2:1 ratio, slow cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.36g) of Example 2 and tetrakis(dimethylsiloxy)silane (0.07 mL) wasdissolved in 1 mL of dry toluene and various amounts of carbon nanotubes(0.01 to 20 weight %) were added with stirring. With continued stirring,a slow cure catalyst (10 μL of a 2-2.5%platinum-cyclovinylmethylsiloxane complex in xylene solution) was added.The mixture was transferred to a silicone mold and was allowed to gel atroom temperature (5 minutes). The sample was post cured above 100° C. tocompletely cure the resin. The result was an opaque elastomeric samplewhich had good thermal and oxidative stability and retained >40% weightafter heating under air to 1000° C.

Example 18

Formulation of clay compositions from a catalytic hydrosilylationreaction of 2:1 oligomeric vinyl silane terminated resin based onbisphenol-A and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy)silane (2:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.35g) of Example 2 and tetrakis(dimethylsiloxy)silane (0.07 mL) wasdissolved in 1 mL of dry toluene and various amount of clay (hydratedaluminum silicate; 0.01 to 20 weight %) were added with stirring. Withcontinued stirring, a rapid cure catalyst (15 μL of a 2-2.5%platinum-vinylmethylsiloxane complex in xylene solution was added. Themixture was transferred to a silicone mold and was allowed to gel atroom temperature (5 seconds). The sample was post cured above 100° C. tocompletely cure the resin. The result was an opaque elastomeric samplewhich had good thermal and oxidative stability and retained >40% weightafter heating under air to 1000° C.

Example 19

Formulation of carbon nanofiber compositions from a catalytichydrosilylation reaction of 2:1 oligomeric vinyl silane terminated resinbased on bisphenol-A and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy)silane (2:1 ratio, slow cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.40g) of Example 2 and tetrakis(dimethylsiloxy)silane (0.10 mL) wasdissolved in 1 mL of dry toluene and various amounts of carbonnanofiber-s (0.01 to 20 weight %) were added with stirring. Withcontinued stirring, a slow cure catalyst (15 μL of a 2-2.5%platinum-cyclovinylmethylsiloxane complex in xylene solution) was added.The mixture was transferred to a silicone mold and was allowed to gel atroom temperature (15 seconds). The sample was post cured above 100° C.to completely cure the resin. The result was an opaque elastomericsample which had good thermal and oxidative stability and retained >40%weight after heating under air to 1000° C.

Example 20

Formulation of a metal oxide compositions from a catalytichydrosilylation reaction of 2:1 oligomeric vinyl silane terminated resinbased on bisphenol-A and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy)silane (2:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.38g) of Example 2 and tetrakis(dimethylsiloxy)silane (0.071 mL) wasdissolved in 1 mL of dry toluene and various amount of powdered antimonyoxide (0.01 to 20 weight %) were added with stirring. With continuedstirring, a rapid cure catalyst (15 μL of a 2-2.5%platinum-vinylmethylsiloxane complex in xylene solution) was added. Themixture was transferred to a silicone mold and was allowed to gel atroom temperature (5 seconds). The sample was post cured above 100° C. tocompletely cure the resin. The result was an opaque elastomeric samplewhich had good thermal and oxidative stability and retained >40% weightafter heating under air to 1000° C.

Example 21

Formulation of microballoon compositions from a catalytichydrosilylation reaction of 2:1 oligomeric vinyl silane terminated resinbased on bisphenol-A and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy)silane (2:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.38g) of Example 2 and tetrakis(dimethylsiloxy)silane (0.07 mL) wasdissolved in 1 mL of dry toluene and various amount of microballoons(0.01 to 20 weight %) were added with stirring. With continued stirring,a rapid cure catalyst (50 μL of a 2-2.5% platinum-vinylmethylsiloxanecomplex in xylene Solution) was added. The mixture was transferred to asilicone mold and was allowed to gel at room temperature (5 seconds).The sample was post cured above 100° C. to completely cure the resin.The result was an opaque elastomeric sample which had good thermal andoxidative stability and retained >40% weight after heating under air to1000° C. and was less dense than Example 3.

Example 22

Synthesis of 2:1 oligomeric vinyl silane terminated resin based on4,4′-difluorobenzophenone (excess) and bisphenol-A—To a 100 mLthree-necked flask fitted with a thermometer, a Dean-Stark trap withcondenser, and a nitrogen inlet were added the oligomeric product fromthe reaction of 2 moles of benzophenone and 1 mole of bisphenol A (3.44g, 5.50 mmol), 4-vinyl(dimethylsilyl)phenol (2.06 g, 11.6 mmol) andpotassium carbonate (5.00 g, 36.2 mmol) in 10 mL of DMF. The mixture washeated to 145° C. for 3 h. The mixture was cooled and poured into waterand extracted with diethyl ether. The solvent was removed in vacuo andthe resulting oil dissolved in 1:1 methylene chloride:hexane andfiltered through a silica plug. The solvent was removed in vacuo and theclear oil vacuum dried to yield the 2:1 oligomeric vinyl silaneterminated resin (4.16 g, 80%). IR [cm⁻¹]: δ3050 (C═CH), 2967 (CH₃),1655 (C═O), 1593 (C═C), 1498 (aromatic), 1242 (C—O), 1171 (C—O), 834(aromatic).

Example 23

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on 4,4′-difluorobenzophenone (excess) andbisphenol-A and tetrakis(dimethylsiloxy)silane (2:1 ratio, slow cure)—Amixture of 0.35 g of vinyl terminated oligomeric monomer from Example 22and tetrakis(dimethylsiloxy)silane (0.07 mL) was dissolved in 1 mL ofdry toluene. While stirring, a slow cure catalyst (30 μL of a 2-2.5%platinum-cyclovinylmethylsiloxane complex in xylene solution) was added.The mixture was transferred to a silicone mold and was allowed to gel atroom temperature (15 min). The sample was post cured above 100° C. tocompletely cure the resin. The result was a transparent elastomericsample which had good thermal and oxidative stability and retained >40%weight after heating Linder air to 1000° C.

Example 24

Synthesis of 2:1 vinyl silane terminated resin based on4,4′-difluorobenzophenone—To a 100 mL three-necked flask fitted with athermometer, a Dean-Stark trap with condenser, and a nitrogen inlet wereadded the 4,4′-difluorobenzophenone (0.85 g, 3.90 mmol),4-vinyl(dimethylsilyl)phenol (1.43 g, 8.00 mmol), and potassiumcarbonate (3.32 g, 24.0 mmol) in 5 mL of DMF. The mixture was heated to130° C. for 16 h, cooled, poured into water, and extracted with diethylether. The solvent was removed in vacuo and the resulting oil dissolvedin 1:1 methylene chloride:hexane and filtered through a silica plug. Thesolvent was removed in vacuo and the clear oil vacuum dried to yield the2:1 oligomeric vinyl silane terminated resin (1.29 g, 61%). IR [cm⁻¹]: δ3050 (C═CH), 2967 (CH₃), 1655 (C═O), 1593 (C═C), 1498 (aromatic), 1242(C—O), 1171 (C—O), 834 (aromatic).

Example 25

Catalytic hydrosilylation reaction from reaction of vinyl silaneterminated resin based on 4,4′-difluorobenzophenone and4-vinyl(dimethylsilyl)phenol cured with tetrakis(dimethylsiloxy)silane(2:1 ratio, rapid cure)—A mixture of 0.20 g of Example 24 andtetrakis(dimethylsiloxy)silane (0.07 mL) was dissolved in 2 mL of drytoluene. While stirring, a rapid cure catalyst (20 μL of a 2-2.5%platinum-vinylmethylsiloxane complex in xylene solution) was added. Themixture was transferred to a silicone mold and was allowed to gel atroom temperature (15 sec). The sample was post cured above 100° C. tocompletely cure the resin. The result was a transparent elastomericsample which had good thermal and oxidative stability and retained >40%weight after heating under air to 1000° C.

Example 26

Synthesis of 2:1 oligomeric vinyl silane terminated resin based onbiphenol and 4,4′-difluorobenzophenone—To a 100 mL three-necked flaskfitted with a thermometer, a Dean-Stark trap with condenser, and anitrogen inlet were added the 2:1 biphenyl/benzophenone based hydroxylterminated aromatic ether oligomer (10.0 g, 18.2 mmol), triethylamine(5.70 ml, 41.2 mmol), and anhydrous tetrahydrofuran (100 mL). Thereaction mixture was cooled by means of an ice bath andvinyl(dimethylchloro)silane (5.66 ml, 40.0 mmol) added dropwise. Theresulting mixture was stirred for 1 h. The mixture was poured into waterand extracted with diethyl ether. The solvent was removed in vacuo andthe resulting oil dissolved in 1:1 methylene chloride:hexane andfiltered through a silica plug. The solvent was removed in vacuo and theclear oil vacuum dried to yield the 2:1 oligomeric vinyl silaneterminated resin (12.1 g, 92%). IR [cm⁻¹]: δ 3051 (C═CH), 2968 (CH₃),1654 (C═O), 1590 (C═C), 1501 (aromatic), 1242 (C—O), 1171 (C—O), 833(aromatic).

Example 27

Catalytic hydrosilylation reaction with 2:1 oligomeric vinyl silaneterminated resin based on biphenol and 4,4′-difluorobenzophenone andtetrakis(dimethylsiloxy)silane (3:1 ratio, rapid cure)—A mixtureformulated from the 2:1 oligomeric vinyl silane terminated resin (0.35g) of example 26 and tetrakis(dimethylsiloxy)silane (0.05 mL) wasdissolved in 1 mL of dry toluene. With stirring, a rapid cure catalyst(6 μL of 2-2.5% platinum-vinylmethylsiloxane complex in xylene solution)was added. The mixture was transferred to a silicone mold and wasallowed to gel at room temperature (10 seconds). The sample was postcured above 100° C. to completely cure the resin. The result was atransparent elastomeric sample which had good thermal and oxidativestability and retained >40% weight after heating under air to 1000° C.

Obviously, many modifications and variations of the present inventionare possible in light of the above teachings. It is therefore to beunderstood that the claimed invention may be practiced otherwise than asspecifically described. Any reference to claim elements in the singular,e.g., using the articles “a,” “an,” “the,” or “said” is not construed aslimiting the element to the singular.

1. A compound having the formula:

wherein each Ar is an independently selected aromatic group; whereineach R is an independently selected alkyl group; wherein n is a positiveinteger; wherein w is 0 or 1; wherein x is 0 or 1; wherein y is 0 or 1;wherein z is 0 or 1; wherein if y is 0 than x and z are 0 and w is 1;wherein if y is 1 than x and z have different values and w equals z. 2.The compound of claim 1, wherein the compound has the formula:


3. The compound of claim 1, wherein the compound has the formula:


4. The compound of claim 1, wherein the compound has the formula:


5. The compound of claim 1, wherein every Ar is a residue of4,4′-dihydroxy-2,2-diphenylpropane;1,1,1,3,3,3-hexafluoro-4,4′-dihydroxy-2,2-diphenylpropane; biphenol; orresorcinol.
 6. A thermoset made by crosslinking a silane-containingcompound with a compound having the formula:

wherein each Ar is an independently selected aromatic group; whereineach R is an independently selected alkyl group; wherein n is a positiveinteger; wherein w is 0 or 1; wherein x is 0 or 1; wherein y is 0 or 1;wherein z is 0 or 1; wherein if y is 0 than x and z are 0 and w is 1;wherein if y is 1 than x and z have different values and w equals z. 7.The thermoset of claim 6, wherein more than one of the compounds havingdifferent values of n are used.
 8. The thermoset of claim 6, whereinevery Ar is a residue of 4,4′-dihydroxy-2,2-diphenylpropane;1,1,1,3,3,3-hexafluoro-4,4′-dihydroxy-2,2-diphenylpropane; biphenol; orresorcinol.
 9. The thermoset of claim 6, wherein the silane-containingcompound is tetrakis(dimethylsiloxy)silane; methyltris(dimethylsiloxy)silane; phenyl tris(dimethylsiloxy)silane;bis[(p-dimethylsilyl)phenyl]ether; diphenylsilane;1,1,3,3-tetramethyldisiloxane;1,1,1,3,3,5,5,7,7-octamethyltetrasiloxane; or hydride-terminatedpolydimethylsiloxane.
 10. The thermoset of claim 6, wherein thecrosslinking occurs both between silane groups and ketone groups andbetween silane groups and vinyl groups.
 11. The thermoset of claim 6,wherein the thermoset further comprises carbon nanotubes, a clay, carbonnanofibers, a metal oxide, or microballoons.
 12. A method comprising:reacting 4,4′-difluorobenzophenone with an aromatic diol to corn anoligomer; and reacting the oligomer with a vinyl dialkylsilane to form acompound having the formula:

wherein each Ar is an independently selected aromatic group; whereineach R is an independently selected alkyl group; wherein n is a positiveinteger; wherein w is 0 or 1; wherein x is 0 or 1; wherein z is 0 or 1;and wherein x and z have different values and w equals z.
 13. The methodof claim 12; wherein the aromatic diol is present in a stoichiometricexcess relative to the 4,4′-difluorobenzophenone; wherein the vinyldialkylsilane is a vinyl(dialkylchloro)silane; and wherein the compoundhas the formula:


14. The method of claim 12; wherein the 4,4′-difluorobenzophenone ispresent in a stoichiometric excess relative to the aromatic diol;wherein the vinyl dialkylsilane is a vinyl(dialkylsilyl)phenol; andwherein the compound has the formula:


15. The method of claim 12, wherein every Ar is a residue of4,4′-dihydroxy-2,2-diphenylpropane;1,1,1,3,3,3-hexafluoro-4,4′-dihydroxy-2,2-diphenylpropane; biphenol; orresorcinol.
 16. The method of claim 12, further comprising: crosslinkinga silane-containing compound with the compound.
 17. The method of claim16, wherein the silane-containing compound istetrakis(dimethylsiloxy)silane; methyl tris(dimethylsiloxy)silane;phenyl tris(dimethylsiloxy)silane; bis[(p-dimethylsilyl)phenyl]ether;diphenylsilane; 1,1,3,3-tetramethyldisiloxane;1,1,3,3,5,5,7,7-octamethyltetrasiloxane; or hydride-terminatedpolydimethylsiloxane.
 18. The method of claim 16, wherein thecrosslinking occurs both between silane groups and ketone groups andbetween silane groups and vinyl groups.
 19. The method of claim 16,further comprising: combining the silane-containing compound and thecompound with carbon nanotubes, a clay, carbon nanofibers, a metaloxide, or microballoons.
 20. A method comprising: reacting4,4′-difluorobenzophenone with a vinyl(dialkylsilyl)phenol to form acompound having the formula:

wherein each R is an independently selected alkyl group.
 21. The methodof claim 20, further comprising: crosslinking a silane-containingcompound with the compound.
 22. The method of claim 21, wherein thesilane-containing compound is tetrakis(dimethylsiloxy)silane; methyltris(dimethylsiloxy)silane; phenyl tris(dimethylsiloxy)silane;bis[(p-dimethylsilyl)phenyl]ether; diphenylsilane;1,1,3,3-tetramethyldisiloxane; 1,1,3,3,5,5,7,7-octamethyltetrasiloxane;or hydride-terminated polydimethylsiloxane.
 23. The method of claim 21,wherein the crosslinking occurs both between silane groups and ketonegroups and between silane groups and vinyl groups.
 24. The method ofclaim 21, further comprising: combining the silane-containing compoundand the compound with carbon nanotubes, a clay, carbon nanofibers, ametal oxide, or microballoons.